At present, in the semiconductor integrated circuits, miniaturization of circuit pattern feature is progressing, and particularly shortening of a gate length of CMOS transistors and reduction of an interconnect pitch are being accelerated. With this, critical dimension accuracy is required for these circuits. The leading resist material used to form presently latest miniature circuit patterns is the so-called chemically amplified resist. The photo acid generation agents which generate acid by exposure are dispersed into the matrix resins, and solubility of the matrix resins is changed by catalytic reaction of acid generated in the exposure section. For example, in the positive tone resist for KrF excimer laser exposure or electron beam (EB) exposure, a (phenolic) hydroxyl group of aqueous base soluble poly hydroxyl styrene resin (PHS) is replaced with a suitable non-polar protection group broken away from acid-catalyzed reaction to make it alkali non-solubility. In addition, the protection group is subjected to de-protection reaction by acid generated in the exposure section to thereby change polarity of the exposure section to make it soluble in alkali development liquid, thus realizing the positive type. Further, in ArF, for example, cyclic-olefin/acrylate copolymers are made to be matrix resin, its polarity group (soluble) is protected by suitable and non-polarity group in a manner similar to KrF to make it non-soluble, which is subjected to de-protection by an acid catalyst to make to soluble. In the general chemically amplified positive resist on the basis of the de-protection reaction, one high molecule is a copolymer (m+n) of m numbers of protected monomer and n numbers of de-protected monomer. When the protection rate m/(m+n) is to be smaller than a predetermined value by the acid catalyzed reaction, solubility increases rapidly.
On the other hand, as the negative-tone reaction mechanism, a cross linking type and a polarity change type are known. In the cross linking type, a cross linker molecule having a plurality of reaction groups coupled to high molecules constituting a resist matrix (a main element constituting a resist film) by the acid catalyst reaction in addition to the above-described acid generation agent is dispersed into the resist. The high molecules are connected together through the cross linking agent by catalyst reaction of acid generated in the exposure section to increase the molecular weight (further resulting in gel-formation), thus being hard to be soluble into a development liquid. As the polarity change type, a polymer or a molecule including a reaction group which changes from polarity to non-polarity by the acid catalyst reaction is known. As such a reaction as described, a pinacol rearrangement reaction and a lactone formation reaction are used.
Further, a resist, with molecules such as calixarane, fullerene, dendrimer, cyclodextrine or the like other than high polymers, used as matrix, has been also proposed and studied. Furthermore, it has been also proposed that the above materials are used to constitute a chemically amplified resist. The calixarane, fullerene, and dendrimer have been discussed in for example, Journal of Photopolymer Science and Technology, Vol. 13, No. 3 (2000), pp. 413-418, Journal of Photopolymer Science and Technology, Vol. 14, No. 4 (2001) pp. 543-546, and Journal of Photopolymer Science and Technology, Vol. 13, No. 2 (2000) pp. 339-344, respectively.